Absorbent material

ABSTRACT

This invention relates to absorbent materials useful in the manufacture of absorbent articles, in particular dressings for the advanced wound care market. The absorbent materials of the present invention are sulfonated polysaccharides, particularly water-insoluble cellulose alkyl sulfonates in which the cellulose is substituted by one type of alkyl sulfonate group. The invention also provides a process for the manufacture of such materials. The preferred cellulose alkyl sulfonate described herein is cellulose ethyl sulfonate. Reinforcing fibers and/or antimicrobial agents are optionally applied to the cellulose alkyl sulfonate.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to and is a Continuation of U.S. patentapplication Ser. No. 12/574,322, filed on Oct. 6, 2009, which claimspriority to United Kingdom Patent Application, GB 0821675.6, filed onNov. 27, 2008, and European Patent Application, 08171355.4, filed onDec. 11, 2008, each of which are incorporated herein by reference intheir entirety.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

Not applicable.

BACKGROUND OF THE INVENTION

Absorbent fibers useful as components in advanced wound care dressingsare known in the art, particularly fibers based on alginic acid,carboxymethylcellulose, and carboxymethylchitosan, and salts thereof.

Dressings based on fibers of alginic acid or its salts have good overallabsorbency of wound fluid, but suffer from slow absorption due to theneed to exchange multivalent ions binding the fibrous structure togetherwith sodium ions present in wound fluid. Although this ion exchangerenders the fibers swellable in ion containing aqueous media, allowingsignificant absorption of fluid, the mechanical strength of the gelledfibers is compromised, and it is not routinely possible to remove asaturated dressing in one piece. Frequently, the dressing must beirrigated with saline to wash it away, and this can be traumatic for thepatient.

Carboxymethyl cellulose fibers have also been used as the main componentin advanced wound care dressings, and these too have significantabsorptive capacity for wound fluid. Their advantage over alginate-typedressings is that absorption of fluid is virtually instantaneous sinceno ionic exchange is required to render the fibers gellable. Inaddition, those fibers based on a highly crystalline cellulose, such aslyocell, and in particular those described in EP0616650 and EP0680344,tend to retain a higher level of mechanical strength and therefore maybe removed from the wound site in one piece. However the absorptivecapacity of this class of material is strongly dependent on the pH ofthe wound fluid, reducing dramatically at acidic pH. This is a seriousdrawback since chronic wound fluid pH can range between 4 and 8depending on the state of healing. Furthermore, it has been recognizedthat artificially lowering the pH of the wound environment may lead toimproved healing outcomes. For instance, it has been found (Tsioras etal, article presented at 19th Annual Symposium on Advanced Wound Care,San Antonio, Tex., Apr. 30, 2006-May 3, 2006) that applying a wounddressing containing a pH adjusting cream of pH 2.8 decreased the time ittook for the wound to close. In another study, burn wounds healedquicker when treated with fluid having a pH of 3.5 (Kaufman et al.,Burns Incl Therm Inj, 12(2) 84-90 (1985)). Indeed, preparations arecommercially available for use in conjunction with absorbent dressingsto reduce the pH of the wound environment. For instance, CADESORB®available from Smith & Nephew has a pH of about 4.35.

It is desirable for an absorbent dressing to perform well at acidic pH,and preferably for it to perform well over a wide range of pH. Sinceabsorbent dressings based on carboxymethylcellulose do not perform wellin low pH environments, there is a need for an instantly gelling,absorptive dressing that continues to absorb to a good level at reducedpH.

It is desirable for absorbent fibers for use in absorbent dressings tobe obtained from a renewable resource, to be inexpensive and alsobiodegradable. Hence, there is considerable interest in cellulose as arenewable and biodegradable source of absorbent material. U.S. southernpine fluff pulp is used as an absorbent material in the personal careindustry. However, it is commonly used in conjunction with otherabsorbent materials, and commonly materials that are not renewable andbiodegradable, for example acrylic acid polymers. The reason for this isthat absorbed liquid is not effectively retained in materials that aremade exclusively of cellulosic fibers.

The cellulose fiber can be modified by sulfonation, for example bysubstitution with an alkyl sulfonate at one or more of the hydroxylgroups on the anhydroglucose monomers that make up the cellulosebackbone, forming ether linkages. Cellulose derivatives of this type areknown as cellulose sulfonates or cellulose alkyl sulfonates.

Commercially available cellulose ethers are, as a rule, water-solublecompounds. In particular, cellulose ethyl sulfonate is known to bewater-soluble.

Herzog et al., U.S. Pat. No. 4,990,609 describes cellulose ethylsulfonates of high solution quality, which are prepared by addition tocellulose of an alkylating agent and subsequently addition of alkali.The process is compared to the two-stage process for the production ofcellulose ethyl sulfonate described in SU757540.

Cellulose ether sulfonates have been modified further in order toproduce water insoluble products. For instance Glasser et al., U.S.Published Patent Application No. 2006/0142560 refers to absorbent fibersbased on mixed cellulose alkylsulfonates in which the cellulose issubstituted by two different groups, an alkyl sulfonate and ahydroxyalkyl sulfonate, specifically ethyl sulfonate and 2-hydroxypropylsulfonate. Water insolubility of the modified cellulose is believed toresult from the presence of the 2-hydroxypropyl sulfonate group.

Shet et al., U.S. Pat. No. 5,703,225 refers to a water-insolublesulfonated cellulose that is a hydroxy sulfonic cellulose in which boththe sulfur atom of a sulfonic group and a hydroxyl group are directlyattached to a carbon atom on the cellulose chain.

To be suitable for use in wound dressings, absorbent materials mustretain their integrity and hence be water-insoluble. The principaldisadvantage of the water insoluble cellulose alkyl sulfonates that havebeen developed for use as absorbent materials to date is the requirementfor substitution of the cellulose with at least two different groups.Compared to substitution with a single substituent, additional reactantsand additional processing steps are not desirable, and are likely toincrease the cost of manufacture. Furthermore, as the cellulose isincreasingly modified, benefits associated with the natural fiber, suchas its biodegradability, may be impaired.

SUMMARY OF THE INVENTION

It has surprisingly been found that water-insoluble cellulose alkylsulfonates may be prepared by the substitution of cellulose with onlyone type of alkyl sulfonate.

It will be clear to those skilled in the art that other polysaccharidesubstrates could be converted to an alkyl sulfonate derivative inaccordance with the invention. For example, chitin and chitosan arenatural polysaccharides based on D-glucosamine units, which havehydroxyl groups at positions at C3 and C5 where reaction substitutionwith alkyl sulfonate groups can take place. In addition, it is possibleto substitute at the amine group in the C2 position, attaching the alkylsulfonate via the nitrogen.

Thus, according to a first aspect of the invention, there is provided anabsorbent article comprising as an absorbent material, a water-insolublepolysaccharide alkyl sulfonate, wherein the polysaccharide issubstituted with one type of alkyl sulfonate.

The modified polysaccharides of the invention are highly advantageousfor use as absorbent materials in wound dressings because they exhibitexcellent absorption and retention of fluid while maintaining theirintegrity sufficiently to be removed from the wound site in one piece,without irrigation, and with minimum pain and shedding. As withcarboxymethyl cellulose, absorption of fluid is virtually instantaneoussince ionic exchange is not required for the fibers to become gellable.However, the water-soluble polysaccharide alkyl sulfonates of thepresent invention are advantageous compared to carboxymethyl cellulosebecause the absorptive capacity may be affected to a lesser extent bychanges in pH. Wound dressings containing these materials may continueto absorb to a good level at low pH.

The polysaccharide alkyl sulfonate may be used in the form of fibers.

The polysaccharide alkyl sulfonate may be a cellulose alkyl sulfonate,and the following description refers primarily to such embodiments ofthe invention. It will be appreciated, however, that otherpolysaccharides may be utilized.

The alkyl moiety of the alkyl sulfonate substituent group is preferablya lower alkyl having 1 to 6 carbon atoms, preferably methyl, ethyl,propyl, or butyl. The alkyl moiety may be branched or unbranched, andhence suitable propyl sulfonate substituents may be 1- or2-methyl-ethylsulfonate. Butyl sulfonate substituents may be2-ethyl-ethylsulfonate, 2,2-dimethyl-ethylsulfonate, or1,2-dimethyl-ethylsulfonate. The alkyl sulfonate substituent group thatis most preferred is ethyl sulfonate.

Thus, a preferred cellulose alkyl sulfonate of the present invention iscellulose ethyl sulfonate, where ethyl sulfonate or one of its salts isattached via one or more of the hydroxyl groups on the anhydroglucoseunits of the cellulose. The structure of one anhydroglucose unitsubstituted by one ethyl sulfonate group is depicted by formula (I)

Formula (I) is not meant to depict the exact chemical structure ofcellulose ethyl sulfonate prepared in accordance with the invention,because substitution can take place at any of the hydroxyl positions inthe cellulose macromolecule, in any distribution up to the maximumdegree of substitution that is possible.

The average degree of substitution refers to the mean number of hydroxylpositions substituted with an alkyl sulfonate substituent group, or putanother way, the mean number of moles of alkyl sulfonate groups per moleof anhydroglucose unit in the cellulose polymer. The maximum degree ofsubstitution is therefore 3, when the anhydroglucose unit is substitutedat all three hydroxyl positions. The degree of substitution when anaverage of one hydroxyl group is substituted per anhydroglucose unit, asshown in Formula (I), is 1.

Cellulose ethyl sulfonate is described in the prior art as awater-soluble compound, and is modified further to render itwater-insoluble, e.g., by alkylation with 3-chloro-2 hydroxypropylsulfonate. Water insoluble cellulose ethyl sulfonate and other insolublecellulose alkyl sulfonates wherein the cellulose is substituted with onetype of alkyl sulfonate are therefore believed to be novel.

Thus, in another aspect of the invention, there is provided awater-insoluble cellulose alkyl sulfonate, wherein the cellulose issubstituted with one type of alkyl sulfonate.

The functional properties of the cellulose alkyl sulfonates of thepresent invention depend on the degree of substitution, the chain lengthof the cellulose backbone structure, and the structure of the alkylsulfonate substituent. Solubility and absorbency are largely dependenton the degree of substitution: as the degree of substitution isincreased, the cellulose alkyl sulfonate becomes increasingly soluble.It follows that, as solubility increases, absorbency increases.

To be useful in an absorbent advanced wound dressing, the fibers of theabsorbent material preferably have an absorbency of at least 8 grams pergram (g/g) of 0.9% saline solution, as measured by the method describedbelow in Example 1. The fibers of the preferred cellulose alkylsulfonates of the present invention have an absorbency (of 0.9% salinesolution) of at least 8 g/g, more preferably at least 9 g/g, mostpreferably at least 10 g/g.

Another class of woundcare dressings, those which simply provide anon-adhesive wound contact layer, sometimes known as Tulle, do notrequire such a high level of absorbency since they may be used on woundsthat exhibit a lower level of wound exudate generation, or a moreabsorbent layer is used on the top surface of the contact layer. Howeverthe key attribute of such contact layers is that they do not adhere tothe wound bed. A fabric material comprising cellulose alkyl sulfonatefibers with a fabric absorbency greater than 2 g/g provides for a goodcontact layer dressing as the fibers absorb sufficient exudate, thusforming a gelled material to provide a non-adhesive surface. Thus, inanother aspect, cellulose alkyl sulfonates of the present invention havean absorbency (of 0.9% saline solution) of greater than 2 g/g, 4 g/g, or6 g/g.

It has been found that the average degree of substitution shouldpreferably be less than 0.4 for the cellulose alkyl sulfonate to besubstantially water-insoluble. By “substantially” is meant in thiscontext that when the cellulose alkyl sulfonate is exposed to an excessof an aqueous medium it does not dissolve into solution, or at leastthat dissolution is so low as to have no significant effect on theproperties of the polymer.

The average degree of substitution is preferably less than 0.4, morepreferably less than 0.3. In some preferred embodiments of theinvention, the average degree of substitution of the cellulose alkylsulfonate is from about 0.05 to about 0.4, more preferably from about0.1 to about 0.3.

Cellulose alkyl sulfonates with alkyl group having 2 to 6 carbon atomsaccording to the present invention can be formed by reaction ofcellulose with an alkenyl sulfonate or one of its salts in the presenceof a base, preferably an alkali metal hydroxide, either in aqueous ornon-aqueous medium. Cellulose alkyl sulfonate with 1 carbon atom, i.e.,cellulose methylsulfonate, can be formed by reaction with chloromethanesulfonic acid or one of its salts in the presence of a base, preferablyan alkali metal hydroxide, either in aqueous or non-aqueous medium.

Alkalization and alkyl sulfonation (which in this case is anetherification step) may be carried out as a single step in which thebase and alkenyl sulfonate or chloromethylsulfonate are added at thesame time in one reaction vessel (a “one-pot” process). Alternatively,alkalization and alkyl sulfonation may be carried out in two separatereaction steps, treating the cellulose first with alkali and then alkylsulfonating agent, or with alkyl sulfonating agent and then alkali.

One-pot processes are often desirable because they can be easier,quicker, and by minimizing the number of reaction steps a higher yieldmay be obtained.

When the alkali and alkyl sulfonating agent are used simultaneously in aone-pot process, to produce a cellulose alkyl sulfonate of the presentinvention, the reaction rate is higher than that observed for theequivalent reaction in which alkalization and alkyl sulfonation arecarried out in separate steps. As mentioned above, the greater thedegree of substitution, the greater the absorbency of the cellulosealkyl sulfonate material. Thus, the reaction rate may be determined bymeasuring the time taken for the alkyl sulfonation reaction to yield aproduct having a particular degree of absorbency. In practice, it is noteasy to stop a reaction at a specific absorbency level. Nevertheless, itis clear that a reaction taking 90 minutes to reach an absorbency of14.2 g/g is significantly faster than one that takes 120 minutes toreach an absorbency of only 9.7 g/g.

The amount of water in the reaction mixture is also shown to affect thereaction rate. Lowering the water content in a reaction in whichalkalization and alkyl sulfonation are carried out simultaneouslyresults in a significant increase in reaction rate. Lowering the watercontent in the alkyl sulfonation step of a reaction in whichalkalization and alkyl sulfonation are carried out separately increasesthe rate, but to a lesser extent.

A one-pot process would also be expected to minimize exposure of thecellulose to the base, therefore keeping the alkaline, oxidativedegeneration of the cellulose to a minimum. It is necessary to minimizedegeneration of the cellulose during processing in order to ensure thatthe modified cellulose is sufficiently strong to be useful as anabsorbent material in a wound dressing, and indeed to maximize both thedry strength and the wet strength of the product.

However, it has been found that the strength of the fibers prepared by aone-pot process may be surprisingly and significantly weaker than fibersprepared by carrying out alkalization and alkyl sulfonation in separatesteps, depending on the level of water used in the reaction mixture.

When higher levels of water are used in the reaction, the cellulosealkyl sulfonates produced by a one-pot process have a surprisingly lowfiber strength compared to the cellulose alkyl sulfonates produced bythe analogous two-step process. The fibers are too weak to be suitablefor processing using normal non-woven textile processing methods. If thelevel of water used in the reaction is reduced, the reaction rateincreases and also the fiber strength increases to a useable level.

According to a further aspect of the invention, there is provided aprocess for the preparation of water-insoluble cellulose alkyl sulfonatecomprising the simultaneous reaction of cellulose with an alkali andalkyl sulfonating agent, and wherein the weight of water present in thereaction is less than 1030%, preferably less than 1015%, preferably lessthan 950%, of the (dry) weight of the cellulose. Fiber absorbenciesaverage about 15 g/g at 1027% water on a dry weight basis.

According to a further aspect of the invention, there is provided aprocess for the preparation of a water-insoluble cellulose alkylsulfonate, which process comprises the separate steps of:

(a) treating the cellulose with alkali;

(b) reacting the product of step (a) with an alkenyl sulfonate or itssalt, or chloromethane sulfonic acid or its salt; and

(c) isolating the product of step (b).

This two-step process is surprisingly beneficial when the level of waterused in step (b) is more than 950% of the (dry) weight of the cellulose.

In another aspect of the present invention, an absorbent articlecomprising the cellulose alkyl sulfonate fibers is provided. When fullyhydrated, the absorbent article is substantially transparent. This isadvantageous in wound care applications since the state of theunderlying wound can be determined without removing the dressing.

In another aspect, the present invention is directed to an absorbentfabric article comprising cellulose alkyl sulfonate of the presentinvention which is reinforced with a reinforcing fiber blended or bondedto the water-insoluble polysaccharide alkyl sulfonate. The use ofsheath/core bicomponent fibers is particularly advantageous because thesheath material melts at a lower temperature than the core so on bondingleaves a strong, unmelted core superstructure. In the present invention,it was found unexpectedly that when thermoplastic bicomponent fibersbased on polyolefins (preferably a polypropylene core/polyethylenesheath) are used to reinforce cellulose ethyl sulfonate fibers, even upto a level of 20% by weight, the absorbency of the resultant fabric isnot compromised by the substantially non-absorbent, hydrophobicreinforcing component. Moreover, using a reinforcing fiber having alower linear density allows for a reduction in the weight amount of thefibers, resulting in increased transparency of the absorbent article.

In yet another aspect, the absorbent fabric articles comprising thecellulose alkyl sulfonate of the present invention exhibit an absorbencyof at least 15 g/g using a sodium/calcium test solution. Absorbency ispreferably not compromised using a reinforcing fiber, while wet strengthis improved. Thus, the absorbency of the composite product comprisingthe cellulose alkyl sulfonate fibers and the reinforcing fibers ispreferably at least 15, 16, 17, 18, 19, or 20 g/g using thesodium/calcium test solution. The wet strength of the composite productis preferably at least 1, 2, 3, 4, 5, or 6 N/cm when using a sodiumcalcium test solution and Instron tensile testing machine as providedherein.

In still another aspect, one or more antimicrobial agents are applied tothe polysaccharide alkyl sulfonate fibers and absorbent articles of thepresent invention. Preferred agents include silver and/orpolyhexamethylene biguanide (“PHMB”). The weight of the silver cation inthe product is preferably about 0.5 to 5 wt %, preferably about 1 to 3wt %, and still more preferably about 1.5 to 2.0 wt %. The weight ofPHMB is preferably about 0.1 to 1%, and is preferably about 0.5 to 0.7wt %.

Additional aspects of the invention, together with the advantages andnovel features appurtenant thereto, will be set forth in part in thedescription which follows, and in part will become apparent to thoseskilled in the art upon examination of the following, or may be learnedfrom the practice of the invention. The objects and advantages of theinvention may be realized and attained by means of the instrumentalitiesand combinations particularly pointed out in the appended claims.

DESCRIPTION OF THE DRAWINGS

FIG. 1 shows the absorbency of cellulose ethyl sulfonate (“CES”) fibersof the present invention comparable to carboxymethyl cellulose (“MC”)fibers as described in Example 8.

DETAILED DESCRIPTION OF THE INVENTION

Processes for preparing the cellulose alkyl sulfonates of the presentinvention were compared using 47% NaOH solution, 25% sodiumvinylsulfonate solution, and different quantities of water in the alkylsulfonation reaction. The properties of the fibers are presented inTable 1 below:

TABLE 1 Summary of Cellulose Ethyl Sulfonate Time of Weight water inWeight of NaOH in alkylsulfonation alkylsulfonation alkylsulfonationAbsorbency Filament Reaction type (min) (% of fiber wt) (% fiber wt)(g/g) strength Two-step high water 120 970 197 9.7 OK (SFM006/69)Two-step low water 120 460 177 13.7 OK (SFM006/136) One-pot high water90 960 198 14.2 Low (SFM006/148c) One-pot low water 70 630 198 11.9 OK(SFM006/145a)

Comparable amounts of water were used in the two-step high waterreaction and the one-pot high water reaction. The reaction rate of theone-pot process was significantly higher, but the filament strength ofthe cellulose ethyl sulfonate product produced by the one-pot processwas lower than the strength of the fiber produced by the two-stepprocess with separate alkalization and alkyl sulfonation steps. Indeed,the filament strength of the product of the one-pot process was too lowfor the material to be effective for use, as intended, in wound dressingapplications.

In the one-pot process for the preparation of water-insoluble cellulosealkyl sulfonate comprising the simultaneous reaction of cellulose withan alkali and alkyl sulfonating agent, the weight of water present inthe reaction is less than 1050% of the (dry) weight of the cellulose,more preferably less than 950% of the weight of the cellulose, stillmore preferably less than 800% of the weight of the cellulose, morepreferably less than 700% by weight of the cellulose, and mostpreferably less than 650% by weight of the cellulose.

Reducing the level of water in the second alkyl sulfonation step in thetwo-step process is shown to increase the reaction rate. However, it isnot always practicable to carry out that reaction step using lowerlevels of water, as it becomes increasingly difficult to wet thecellulose as the volume of alkyl sulfonate reactant decreases. In anycase, when using lower levels of water in the reaction, the one-potprocess is preferred.

At higher levels of water, the two-step process is most suitable forproducing cellulose alkyl sulfonates of the present invention withadequate fiber strength. Preferably, the weight of water present in thealkyl sulfonation step is more than 650% by (dry) weight of thecellulose, more preferably more than 750% by weight of the cellulose,more preferably more than 850% by weight of the cellulose, and mostpreferably more than 950% by weight of the cellulose.

To be suitable for use in the present invention, the cellulose ispreferably fibrous in nature. The cellulose fibers should have a highdegree of crystallinity and total orientation in order that the fibersmaintain sufficient strength after derivatization to be processed, andthat the resulting material is strong enough for its intended use.

In particular, the use of alkali in the alkalization step can degradethe cellulose backbone, causing chain scission and a reduction in thedegree of polymerization, thereby resulting in the fibers having a lowerstrength after derivatization. The dry strength of the derivatizedfibers must be sufficient to enable processing into woven or nonwovenstructures, and, to be useful as an absorbent material in a wounddressing, the wet strength of the material must be sufficient to allowremoval from the site in one piece.

Fibrous celluloses with a high degree of crystallinity, that areparticularly suitable for use in the invention, include cotton orregenerated cellulose fibers such as lyocell.

It will be clear to those skilled in the art that it is possible tosulfonate particulate cellulose such as pulp fibers, then dissolve thesulfonated cellulose in a suitable solvent, such as a lyocell solvent oran ionic liquid, and spin the sulfonated cellulose as fibers, or extrudethe sulfonated cellulose as a film or other extrusion to produce theabsorbent material of the invention. Furthermore, a blowing agent couldbe added to the solution in order to produce a foamed absorbentmaterial.

The cellulose may be alkalized by treatment with a strong alkali,preferably an alkali metal hydroxide such as sodium hydroxide. A 47%sodium hydroxide solution has been found to be suitable. Generally, thehigher the concentration of alkali and the higher the reactiontemperature, the faster the rate of reaction. The strength of thereaction conditions should be balanced with the need to avoiddegradation of the cellulose substrate. However, the level ofdegradation of the cellulose is considerably lower than might beexpected under the relatively intense reaction conditions that arerequired for alkalization. When carrying out the two-step process, itmay be beneficial to remove excess alkali before proceeding with secondalkyl sulfonation step, e.g., by mechanically squeezing the alkalizedfibers.

In the case of the alkyl sulfonation step (or etherification step) with2 to 6 carbon atoms, the reaction involves the nucleophilic addition ofthe alkoxide ion to an alkenyl sulfonate, specifically α-alkenylsulfonate or its salt. The α-alkenyl sulfonate is preferably a loweralkenyl sulfonate, in which the alkenyl moiety has 2 to 6 carbon atoms.Preferably the α-alkenyl sulfonate is vinyl sulfonate, allyl sulfonate(1-propenyl sulfonate), isopropenyl sulfonate (1-methylvinyl sulfonate),1-butenyl sulfonate, 1-methyl allyl sulfonate (1-methyl-1-propenylsulfonate) or 2 methylallyl sulfonate (2-methyl-1-propenyl sulfonate).In a particularly preferred embodiment, the α-alkenyl sulfonate is vinylsulfonate, more preferably the sodium salt of vinyl sulfonate, and hencethe cellulose alkyl sulfonate product is cellulose ethyl sulfonate.

The sodium salt of vinyl sulfonate is commercially available as anapproximately 30% aqueous solution. It may be brought into contact withthe cellulose or alkalized cellulose by methods known in the art, forinstance spraying onto the cellulose, or mixing using stirrers. Theconversion to cellulose alkyl sulfonate can take place at anytemperature up to the boiling point of the reaction mixture, or beyondit if a pressurized system is used. The rate of reaction is increased ifthe reaction stage is carried out at elevated temperature. The preferredrange is 30-95° C. to give a useful degree of substitution in aneconomic time. Further, fresh charges of reactant can be introduced atany time throughout the reaction. The degree of substitution can becontrolled by control of reaction temperature and, in particular, bycontrol of the reaction time.

Vinyl sulfonate is thought to be less hazardous than some of thehalogenated reactants, particularly chlorinated reactants, which aretypically used to prepare the absorbent materials currently availablefor use in wound care products. Certainly, chloroacetic acid, used inthe manufacture of carboxymethyl cellulose, is a potentially dangerousalkylating agent. Its use during the manufacturing process isundesirable, and retention of any residual chloroacetic acid in theabsorbent product may be harmful, at the least causing skin irritation.The use of only one type of alkyl sulfonate also presents potentialadvantages in terms of safety and removal of residual reactant comparedto other water-insoluble cellulose alkyl sulfonates that are known, inwhich the cellulose is substituted with more than one type of alkylsulfonate, if only because of the relative simplicity of the chemistry.

After the reaction has proceeded to the desired extent, the reaction canbe stopped by neutralizing the reaction mixture, i.e., reducing the pHto approximately neutral by addition of acid. The acid may be any commonmineral or organic acid such as hydrochloric or acetic acid,respectively. The cellulose alkyl sulfonate product can then be washedfree of by-products and impurities by employing washing stages known inthe art. Such stages include washing with water, organic liquids, ormixtures thereof. Particularly useful are mixtures of a lower alcoholand water. Washing efficiency can be enhanced by washing at elevatedtemperature. After washing, it may be desirable to apply a processingaid, such as glycerol, as is common practice in the production of, forexample, cellulose film (cellophane). This can be achieved by methodsknown in the art, such as dipping, spraying etc.

Finally the derivatized cellulose article should be dried to removeresidual liquid from the previous stages. Drying can be carried out bymethods known in the art such as forced air drying, radiant heat dryingetc.

The absorbent materials of the present invention exhibit instant gellingin aqueous media, good absorbency and, crucially, good retention ofabsorbency in an acidic environment. This renders them ideal for use asan absorbent wound dressing, or as part of an absorbent dressing. Theyare particularly useful for wounds with moderate to high levels ofexudates, and for flat or cavity wounds of this type. Typical examplesinclude pressure sores and leg ulcers.

The use of the absorbent materials of the present invention is notlimited to wound care products, and they are expected to be useful formany other applications. Their absorbent properties, biodegradability,and the fact that cellulose is a renewable material, mean that thecellulose alkyl sulfonates of the invention are also particularlydesirable for use in the personal care sector, particularly fordisposable sanitary articles such as nappies (diapers), disposablenappies and training pants, feminine care products, e.g., tampons,sanitary towels, or napkins and pant liners, and incontinence products.The simplicity of the chemistry and the availability of the reactantsenable the cost of manufacture of such articles to be keptadvantageously low.

Other medical products are envisaged, for example, surgical and dentalsponges. The materials could also be useful in packaging, for example asabsorbent pads in food containers.

The cellulose alkyl sulfonates of the present invention may be processedaccording to known methods into a wide variety of forms, depending ontheir intended use. The manner in which the derivative cellulose isprocessed has a significant effect on the properties of the finalproduct, particularly the strength, gelling time, and absorbency.Preferred cellulose alkyl sulfonate products for use in wound carearticles are carded, needle-bonded nonwovens.

The cellulose alkyl sulfonates may be combined with one or morereinforcing fibers as generally set forth in Hansen, U.S. Pat. No.5,981,410 titled “Cellulose-Binding Fibres”; Stengaard et al., U.S. Pat.No. 6,811,716 titled “Polyolefin Fibers and Method for the ProductionThereof”, Jensen et al., U.S. Pat. No. 5,958,806 titled “CardableHydrophobic Polyolefin Fibres Comprising Cationic Spin Finishes;” all ofwhich are incorporated by reference. Preferred reinforcing fibers arethermoplastic biocomponent fibers, most preferably having a polyolefincomponent. Thus, the fibers preferably comprise a polyolefin-containingpolymeric material of which the largest part (by weight) consists ofhomo- or copolymers of monoolefins such as ethylene, propylene,1-butene, 4-methyl-1-pentene, etc. Examples of such polymers areisotactic or syndiotactic polypropylene, polyethylenes of differentdensities, such as high density polyethylene, low density polyethylene,and linear low density polyethylene and blends of the same. Thepolymeric material may be mixed with other non-polyolefin polymers suchas polyamide or polyester, provided that polyolefins still constitutethe largest part of the composition. The melts used to produce thepolyolefin-containing fibers may also contain various conventional fiberadditives, such as calcium stearate, antioxidants, process stabilizers,compatibilizers, and pigments. Methods for applying the thermoplasticbiocomponent fibers are described in EP0740554; EP0171806; Ejima et al.,U.S. Pat. No. 5,456,982; Davies, U.S. Pat. No. 4,189,338; Davies, U.S.Pat. No. 3,511,747; and Reitboeck et al., U.S. Pat. No. 3,597,731, whichare incorporated by reference.

The thermoplastic bicomponent fibers may be of the sheath-core type withthe core being located either eccentrically (off-center) orconcentrically (substantially in the center), or of the side-by-sidetype, in which each of the two components typically has a semi-circlecross section. Bicomponent fibers having irregular fiber profiles arealso contemplated, e.g., an oval, ellipse, delta, star, multilobal, orother irregular cross section, as well as splittable fibers. Thebicomponent fibers will typically have a high melting and low meltingpolyolefin component which comprise, respectively,polypropylene/polyethylene (the polyethylene comprising HDPE, LDPE,and/or LLDPE), high density polyethylene/linear low densitypolyethylene, polypropylene random copolymer/polyethylene, orpolypropylene/polypropylene random copolymer. Preferred thermoplasticbiocomponent fibers are commercially available from Fiber Visions(Athens, Ga.). Suitable thermoplastic biocomponent fibers comprise 30,25, 20, 18, 16, 14, 12, 10, 8, 6, or 4 wt % or any range there betweenof the composite absorbent article. The thermoplastic biocomponentfibers preferably have a linear density of about 1.7, 1.9, 2.1, 2.3,2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.8, 4.0, 4.2, 4.4, 4.6, 4.8, 5.0 decitexup to 16.7 decitex or any range therebetween. However, it has beensurprisingly discovered that when high-density fibers (e.g., 4.0decitex) are incorporated into the absorbent article comprising thecellulose alkyl sulfonate at high levels (e.g., about 20%), theabsorbency of the article is not compromised. Moreover, using areinforcing fiber having a lower linear density allows for a reductionin the weight amount of the fibers, resulting in increased transparency.Thus, in one aspect, the thermoplastic biocomponent fibers preferablycomprise about 10 to 30 wt % (more preferably about 10 to 20%, and stillmore preferably about 10 to 13%) of the absorbent article and have alinear density of about 1.7 to 4.0 decitex (more preferably about 1.7 to1.9 decitex). The temperature used to fuse the fibers together istypically in the range of 90 to 162° C., preferably about 120 to 125° C.

In another aspect, the reinforcing fibers comprise lyocell fibers. Thesefibers generally comprise a cellulose obtained by an organic solventspinning process. Preferably, the lyocell fiber is generated fromcellulose fibers using various amine oxides as solvents. In particular,N-methylmorpholine-N-oxide (“NMNO”) with water (about 12%) proves to bea particularly useful solvent. Examples of processes for preparinglyocell fibers are described in McCorsley et al., U.S. Pat. Nos.4,142,913; 4,144,080; 4,211,574; 4,246,221; and 4,416,698, and others.Jurkovic et al., U.S. Pat. No. 5,252,284 and Michels et al., U.S. Pat.No. 5,417,909 deal especially with the geometry of extrusion nozzles forspinning cellulose dissolved in NMMO. Brandner et al., U.S. Pat. No.4,426,228, is exemplary of a considerable number of patents thatdisclose the use of various compounds to act as stabilizers in order toprevent cellulose and/or solvent degradation in the heated NMMOsolution. Franks et al., U.S. Pat. Nos. 4,145,532 and 4,196,282, dealwith the difficulties of dissolving cellulose in amine oxide solventsand of achieving higher concentrations of cellulose. All of thesepatents are incorporated herein by reference. One lyocell productproduced by Lenzing is presently commercially available as TENCEL®fiber. The methods for including these cellulose fibers into nonwovenstructures to aid in integrity of the product is well known, see, e.g.,GB1207352, which is incorporated by reference. In one aspect, thelyocell fibers comprise 26, 24, 22, 20, 18, 16, 14, 12, 10, 8, 6, or 4wt % or any range therebetween of the composite absorbent article. Thelyocell fibers preferably have a linear density of about 0.7, 0.9, 1.1,1.3, 1.5, 1.7, 1.9, 2.1, 2.3, 2.4, 2.6, 2.8, 3.0, 3.2, 3.4, 3.8, 4.0,4.2, 4.4, 4.6, 4.8, 5.0, 10, 15, 20, 25, up to 30 decitex or any rangetherebetween. As shown in the examples below, it has been surprisinglydiscovered that when low density fibers (e.g., about 1.2 to 1.6 decitex)are incorporated into the composite absorbent article at high levels(e.g., about 10 to 30 wt %, preferably about 10 to 20 wt %), the wetstrength is improved while absorbency is not compromised.

In still another aspect, one or more antimicrobial agents are applied tothe cellulose alkyl sulfonate of the present invention. Preferred agentsinclude silver and/or polyhexamethylene biguanide (“PHMB”).

The present invention is also directed to a novel method for applying ametal ion to a hydrophilic, amphoteric, or anionic polymer, especiallythose used in a medical device, a wound dressing, or an ostomy device.Materials which are particularly adapted for the inventive methodinclude gel-forming fibers such as AQUACEL® (WO 93/12275, WO 94/16746,WO 99/64079, and U.S. Pat. No. 5,731,083), or those described in WO00/01425 or PCT/GB 01/03147; wound dressings containing similargel-forming fibers behind or overlying a non-continuous or perforatedskin-contact layer such as VERSIVA® (U.S. Pat. No. 5,681,579, WO97/07758, and WO 00/41661); DUODERM® (U.S. Pat. No. 4,538,603), DuoDermCGF™ (U.S. Pat. No. 4,551,490 and EP 92 999), or a blend of two or morefibers such as CARBOFLEX® (WO 95/19795). The present invention iswell-suited for other materials which contain carboxymethylcellulose andthe cellulose alkyl sulfonate of the present invention.

Polymers suitable for the present invention include, but are not limitedto, polysaccharides or modified polysaccharides, polyvinylpyrrolidone,polyvinyl alcohols, polyvinyl ethers, polyurethanes, polyacrylates,polyacrylamides, collagen, gelatin, or mixtures thereof. In preferredembodiments, the polymers contain carboxymethylcellulose such as sodiumcarboxymethylcellulose. In one embodiment, the polymer can be apolysaccharide comprising a carboxymethylcellulose or alginate, or amixture of carboxymethylcellulose and alginate. The coating step is mostpreferably used with the cellulose alkyl sulfonate of the presentinvention.

The invention will now be illustrated by the following non-limitingexamples.

Example 1 Method for Determination of the Free Absorbency of Fibers

The fiber was cut into a 2-3 mm flock, and 0.5 g of cut fiber was placedin a 100 ml screw-top jar. 50 ml of test liquid (e.g., 0.9% saline,typically used to simulate the ionic strength of wound fluid) was added,and the jar shaken for 30 seconds to disperse the flock. The dispersionwas then filtered through a 47 mm Buchner funnel fitted with a 42.5 mmdiameter Whatman No. 4 filter paper, using a vacuum pump, with vacuumset to be greater than 0.8 bar for one minute. Then the fiber dispersionwas removed and weighed. Fiber free absorbency was calculated using thefollowing formula:

${{absorbency}{\mspace{11mu} \;}\left( {g/g} \right)} = {\left\lbrack \frac{{wet\_ dispersion}{\_ weight}\; (g)}{{dry\_ flock}{\_ weight}\; (g)} \right\rbrack - 1}$

Example 2 Method for Determination of Breaking Tenacity and Elongationof Single Filaments

Tenacity and elongation at break of dry, single filaments was carriedout using a tensile testing machine, fitted with appropriate jaws forgripping single filaments and load cell of the appropriate range.

The samples were conditioned for at least four hours and were tested inthe standard atmosphere for testing textiles (20±2° C. and 65±2%relative humidity).

The machine was balanced and calibrated according to the manufacturer'sinstructions. Filaments were taken at random from different parts of thesample. The linear density of the filament was measured by anappropriate technique such the Vibraskop method. The filament was thenplaced between the jaws of the tensile testing machine and the teststarted. The following conditions were used:

-   -   Test length: 20 mm    -   Load range: 0-10 cN    -   Cross-head speed: 10 mm/minute    -   Chart speed (when applicable): 10-20 mm/minute    -   Number of tests: 10

After rupture, the crosshead was returned, and the broken ends offilament were checked and removed from the jaws. A note was made if thenumber of jaw breaks exceeded 10%.

The breaking load (cN) and the breaking extension (%) of each filamentwas usually printed out together with the statistics. In the case ofindividual breaking loads being printed out, individual tenacity resultsor a mean tenacity were calculated by hand, as follows:

mean tenacity (cN/tex)=mean breaking load in cN×10 mean linear densityin dtex

Example 3 Preparation of Cellulose Ethyl Sulfonate Using a Two-StepProcess

A 3 g sample of lyocell tow, known under the tradename TENCEL®(manufactured by Lenzing), was immersed in aqueous 47% sodium hydroxidefor 25 minutes at 25° C. Excess sodium hydroxide was then removed bysqueezing. Then 25 ml 30% sodium vinyl sulfonate solution (FlukaChemicals) was added to the fiber and heated at 91° C. for 90 minutes.After this time the reaction mixture was neutralized to pH 7 by addingglacial acetic acid dropwise. Then the excess liquid was squeezed fromthe fiber, and the fiber was washed twice in a mixture of industrialmethylated spirit (“IMS”) and water (80:20 v/v). After drying toconstant weight at 60° C., the fiber was tested for absorbency.

Using the method outlined in Example 1, and an aqueous solution of 0.9%NaCl as the test liquid, an fiber free absorbency value of 11.1 g/g wasachieved.

Example 4 Preparation of Cellulose Ethyl Sulfonate Using a Two-StepProcess (SFM006/69)

A 2.5 g sample of TENCEL® fiber was immersed in 47% sodium hydroxide for30 minutes at 20° C., after which excess liquid was removed bysqueezing. 21 ml sodium vinyl sulfonate (30% aqueous solution) waspoured over the fiber. The vessel containing fiber and reactant was thenheated at 83° C. for two hours, after which time the sample wasneutralized by the dropwise addition of glacial acetic acid until a pHof 7 was reached. The excess liquid was then squeezed from the fiber,and the fiber was washed twice with IMS/water (80:20 v/v), and finallyin 100% IMS. After drying to constant weight at 60° C., the fiber wastested for absorbency according to the method in Example 1, using 0.9%aqueous NaCl as the test liquid. A fiber free absorbency value of 9.7g/g was obtained.

Example 5 Preparation of Cellulose Ethyl Sulfonate Using a One-PotProcess with High Water Content

3 g TENCEL® fiber was immersed in a mixture of 10 ml 47% NaOH and 25 ml30% sodium vinylsulfonate solution, and heated for 75 minutes at 83° C.The reaction mixture was then neutralized by addition of acetic acid,after which the fiber was removed and washed in a mixture of IMS/water(80:20 v/v), and finally in 100% IMS. Drying was carried out at 60° C.

Using the method outlined in Example 1, and an aqueous solution of 0.9%NaCl as the absorbent test liquid, a fiber free absorbency value of 6.6g/g was achieved. The fibers were visibly weaker than the fibers ofExample 6, despite having a lower degree of substitution, as evidencedby the lower absorbency value.

Example 6 Preparation of Cellulose Ethyl Sulfonate Using a One-PotProcess with Low Water Content (SFM006/145a)

3 g TENCEL® fiber was immersed in a mixture of 13 ml 30% sodiumvinylsulfonate solution and 10 ml 47% NaOH solution, and heated for 70minutes at 83° C. The reaction mixture was then neutralized by additionof acetic acid, after which the fiber was removed and washed in amixture of IMS/water (80:20 v/v), and finally in 100% IMS. Drying wascarried out at 60° C.

Using the method outlined in Example 1, and an aqueous solution of 0.9%NaCl as the test liquid, an fiber free absorbency value of 11.9 g/g wasachieved.

Example 7 Comparative Absorbency Test for Underivatized Cellulose

TENCEL® fiber from the same batch used as the starting material forExamples 3 and 4 was subjected to the absorbency test outlined inExample 1, using 0.9% aqueous NaCl as the absorbent test liquid. A fiberfree absorbency value of 0.9 g/g was obtained.

Example 8 Comparison of the Absorbency at Low pH of Cellulose EthylSulfonate Fibers of the Present Invention with Carboxymethyl CelluloseFibers of the Prior Art

The absorbency of carboxymethyl cellulose (CMC) fibers made according tothe teachings in EP 0616650 was measured according to the method ofExample 1 using 0.9% saline solution as absorbing liquid. The pH of thesaline was then reduced successively by addition of 37% HCl and theabsorbency measured again at each pH.

Cellulose ethyl sulfonate fibers were produced according to the presentinvention from lyocell fiber, and their absorbency measured in the sameway at a range of pH values.

The results are shown graphically in FIG. 1. It is clear that celluloseethyl sulfonate fiber of the invention retains significantly more of itsabsorbency at low pH where wound healing is believed to be enhanced.

Example 9 20% by Weight 4.0 Decitex Bicomponent Fiber-ReinforcedCellulose Ethyl Sulfonate Fabric

In this example, cellulose ethyl sulfonate fiber made according to thepresent invention to was cut to 50 mm staple and blended in a 20% byweight proportion with 4.0 decitex 40 mm staple bicomponent fiber(ES-LOWMELT™ manufactured by Fiber Visions) through a sample card. Theresulting web was needlebonded, and then thermally bonded by heating ina recirculating oven set at 125° C. for 10 minutes. Comparativecellulose ethyl sulfonate fabric containing no reinforcing fiber wasmanufactured in a similar manner, without a thermal bonding step.

The wet strength was measured by cutting test specimens 2.5 cm wide×10cm long from the fabric. The sample was mounted in an Instron 3343tensile testing machine to give a gauge length 5 cm. The sample was thenwetted with 2.5 ml of solution A (sodium/calcium solution), left for oneminute, and then tested at 100 mm/min. The sodium/calcium Solution A isformed by dissolving 16.6 g of NaCl and 0.74 g of CaCl dihydrate in 2 Lof water.

The clarity measured subjectively by placing beneath a gelled (0.9%saline hydrated) sample printed bold type face 12 pt Times New Roman andsubjectively scoring the clarity from 0 (completely opaque, typeface notvisible) to 10 (completely clear, undistorted typeface).

The absorbency was measured by weighing a 5 cm×5 cm square of samplematerial (W¹). Next, the sample was placed in Solution A at 37° C. for30 minutes in a petri-dish. Then the square was lifted out of thepetri-dish by holding the square by one corner, and the sample wasallowed to drain for 30 seconds. The sample was then reweighed to obtainthe end weight (W₂). The fabric absorbency is given by W₂−W₁/W₁.

TABLE 2 Summary of Test Results Fabric Wet Absorbency strength (g/g)(N/cm) Clarity CES Fabric 15.9 0.6 9 20% 4.0 decitex bicomponent - 19.75.1 3 reinforced fabric

Example 10 10% by Weight 1.7 Decitex Biocomponent Fiber-ReinforcedCellulose Ethyl Sulfonate Fabric

Cellulose ethyl sulfonate fabric prepared in accordance with the presentinvention containing 10% by weight 1.7 decitex 40 mm staple bicomponentfiber (ES-CURE™ manufactured by Fiber Visions) was manufactured in asimilar manner to Example 9, except the thermal bonding step wasconducted at 135° C., due to the higher melting sheath component. Afabric containing 10% 4.0 decitex ES-LOW MELT™ was also produced as inExample 9. The following table shows the results:

TABLE 3 Test Results Wet strength (N/cm) Clarity 10% 1.7 decitexbicomponent- 2.1 6 reinforced fabric 10% 4.0 decitex bicomponent- 0.6 6reinforced fabric

Example 11 20% by Weight 1.4 Decitex Lyocell-Reinforced Cellulose EthylSulfonate Fabric

In this example, TENCEL® fibers were incorporated at a level of 20% byweight into cellulose ethyl sulfonate nonwoven materials and found thatwet strength is improved significantly, while absorbency is littlecompromised. Cellulose ethyl sulfonate fiber in accordance with thepresent invention was cut to 50 mm staple and blended in a 20% by weightproportion with 1.4 decitex 50 mm staple TENCEL® fiber (manufactured byLenzing AG) through a sample card. The resulting web was needlebonded.The following table shows the results:

TABLE 4 Test Results Fabric Strength absorbency (N/cm) Clarity (g/g)Unreinforced cellulose 0.4 8 19.4 ethyl sulfonate fabric TENCEL ®reinforced cellulose 3.3 5 18.8 ethyl sulfonate fabricThe strength, clarity, and absorbency of the fabric was determined asset forth in Example 9.

Example 12 Silver Alginate Fiber Blend Process

This example describes a blend of silver alginate fibers with celluloseethyl sulfonate fibers using the techniques as generally set forth in WO02/24240, which is incorporated by reference.

Calcium alginate fibers containing approximately 24% by weight silverwere manufactured by immersing calcium alginate fibers in a mixture ofwater/acetone/silver nitrate, followed by washing in acetone/water andfinally acetone before drying the fibers at 50° C. These fibers were cutto 50 mm staple and blended with cellulose ethyl sulfonate staple fibersin such a ratio to give approximately 1.5% silver on weight of dressing,then the blend carded and needle-bonded to give approximately 100 gsmneedled fabric. The fabric had an off-white color on prolonged exposureto light.

In a surface antimicrobial efficacy test known as Qualiscreen, thedressing was found to be antimicrobial, i.e., inhibited formation ofgreater than 99.9% of daughter cells (methicillin resistantStaphylococcus aureus).

Example 13 PHMB Cellulose Ethyl Sulfonate

In this example, a PHMB-loaded cellulose ethyl sulfonate fabric wasproduced by the spray method using a 20% aqueous solution of PHMB togive 0.6% PHMB by weight on dressing. A sample of the dressing wassubjected to the “milk test.” The dressing remained antimicrobial for 72hours, while the control sample became populated with microbes after 24hours.

Example 14 Low Gel Non-Adherent Contact Layer Dressing

Cellulose ethylsulphonate fibers with a fiber absorbency of 4.7 g/g asmeasured by the method in Example 1 were cut to 50 mm staple, thencarded and needled to give a fabric. The absorbency of this fabric wasmeasured by weighing a 5 cm×5 cm square of sample material (W¹). Next,the sample was placed in Solution A (sodium/calcium solution) at 37° C.for 30 minutes in a petri-dish. Then the square was lifted out of thepetri-dish by holding the square by one corner, and the sample wasallowed to drain for 30 seconds, then the sample was reweighed (W₂). Thefabric absorbency is given by W₂−W₁/W₁.

The wet strength was measured by cutting test specimens 2.5 cm wide×10cm long from the fabric. The sample was mounted in an Instron 3343tensile testing machine to give a gauge length 5 cm. The sample was thenwetted with 2.5 ml of solution A (sodium/calcium solution), left for oneminute, and then tested at 100 mm/min.

A highly absorbent fabric from Example 11, prepared from celluloseethylsulphonate fibers with an fiber free absorbency of 12.9 g/g servedas a comparison. The absorbency and tensile strength results are shownin the table below:

TABLE 5 Fabric Strength Absorbency (N/cm) (g/g) Low gel non-adherentcontact layer 1.32 16.8 cellulose ethylsulphonate fabric Highlyabsorbent cellulose 0.4 19.4 ethylsulphonate fabric (Example 11) --unreinforced

It can be seen that absorbency is compromised in the case of the contactlayer fabric, but wet strength is significantly improved. Furthermorethe contact layer fabric exhibited a slippery feel suggesting a lowadherence to skin.

From the foregoing it will be seen that this invention is one welladapted to attain all ends and objectives herein-above set forth,together with the other advantages which are obvious and which areinherent to the invention. Since many possible embodiments may be madeof the invention without departing from the scope thereof, it is to beunderstood that all matters herein set forth or shown in theaccompanying drawing are to be interpreted as illustrative, and not in alimiting sense. While specific embodiments have been shown anddiscussed, various modifications may, of course, be made, and theinvention is not limited to the specific forms or arrangement of partsand steps described herein, except insofar as such limitations areincluded in the following claims. Further, it will be understood thatcertain features and subcombinations are of utility and may be employedwithout reference to other features and subcombinations. This iscontemplated by and is within the scope of the claims.

What is claimed and desired to be secured by Letters Patent is asfollows:
 1. A non-woven absorbent fabric comprising: a gelling fiber;and a reinforcing fiber comprising between 4 and 30 weight percent ofthe fabric, wherein the gelling fiber is blended or bonded with thereinforcing fiber within the non-woven fabric.
 2. The non-wovenabsorbent fabric of claim 1, wherein the absorbency of the fabric is notlower than the absorbency of a fabric comprising the gelling fiberwithout the reinforcing fiber.
 3. The non-woven absorbent fabric ofclaim 1, wherein the absorbency of the fabric is at least 15 g/g.
 4. Thenon-woven absorbent fabric of claim 1, wherein the wet strength of thefabric is at least 0.6 N/cm.
 5. The non-woven absorbent fabric of claim4, wherein the wet strength of the fabric is at least 1 N/cm.
 6. Thenon-woven absorbent fabric of claim 5, wherein the wet strength of thefabric is at least 2 N/cm.
 7. The non-woven absorbent fabric of claim 1,wherein the wet strength of the fabric is greater than the wet strengthof a non-woven fabric comprising the gelling fiber without thereinforcing fiber.
 8. The non-woven absorbent fabric of claim 7, whereinthe reinforcing fiber comprises between 10 and 30 weight percent of thefabric.
 9. The non-woven absorbent fabric of claim 1, wherein thereinforcing fiber has a linear density between 0.7 and 30 decitex. 10.The non-woven absorbent fabric of claim 9, wherein the reinforcing fiberhas a linear density between 0.7 and 4.0 decitex.
 11. The non-wovenabsorbent fabric of claim 1, wherein said reinforcing fiber comprises athermoplastic biocomponent fiber that is thermally bonded to saidgelling fiber.
 12. The non-woven absorbent fabric of claim 1, whereinthe gelling fiber is a polysaccharide fiber.
 13. The non-woven absorbentfabric of claim 12, wherein said reinforcing fiber comprises acellulosic fiber.
 14. The non-woven absorbent fabric of claim 13,wherein said reinforcing fiber comprises a solvent spun cellulose fiber.15. The non-woven absorbent fabric of claim 14, wherein said solventspun cellulose fiber comprises 10 to 30 weight percent of the fabric andhas a linear density of 0.7 to 30 decitex.
 16. The non-woven absorbentfabric of claim 12, where in the gelling fiber is a polysaccharide alkylsulfonate.
 17. The non-woven absorbent fabric of claim 1, wherein thegelling fiber is derived from the group consisting of alginic acid,carboxymethylcellulose, carboxymethylchitosan, and salts thereof. 18.The non-woven absorbent fabric of claim 1, wherein the gelling fiber hasa fiber free absorbency of 0.9% saline solution as a test liquid of atleast 8 g/g.
 19. The non-woven absorbent fabric of claim 1, wherein thegelling fiber has a fiber free absorbency of 0.9% saline solution as atest liquid of at least 2 g/g.
 20. A non-woven absorbent fabriccomprising: a gelling fiber; and a reinforcing fiber, wherein theabsorbency of the fabric is not lower than the absorbency of a fabriccomprising the gelling fiber without the reinforcing fiber.
 21. Thenon-woven absorbent fabric of claim 20, wherein the absorbency of thefabric is at least 15 g/g.
 22. The non-woven absorbent fabric of claim21, wherein the reinforcing fiber has a linear density between 0.7 and30 decitex.
 23. The non-woven absorbent fabric of claim 22, wherein thereinforcing fiber has a linear density between 0.7 and 4.0 decitex. 24.The non-woven absorbent fabric of claim 20, wherein said reinforcingfiber comprises a thermoplastic biocomponent fiber that is thermallybonded to said gelling fiber.
 25. The non-woven absorbent fabric ofclaim 20, wherein the gelling fiber is a polysaccharide fiber.
 26. Thenon-woven absorbent fabric of claim 25, wherein said reinforcing fibercomprises a cellulosic fiber.
 27. The non-woven absorbent fabric ofclaim 26, wherein said reinforcing fiber comprises a solvent spuncellulose fiber.
 28. The non-woven absorbent fabric of claim 27, whereinsaid solvent spun cellulose fiber comprises 10 to 30 weight percent ofthe fabric and has a linear density of 0.7 to 30 decitex.
 29. Thenon-woven absorbent fabric of claim 25, where in the gelling fiber is apolysaccharide alkyl sulfonate.
 30. The non-woven absorbent fabric ofclaim 20, wherein the gelling fiber is derived from the group consistingof alginic acid, carboxymethylcellulose, carboxymethylchitosan, andsalts thereof.
 31. The non-woven absorbent fabric of claim 20, whereinthe gelling fiber has a fiber free absorbency of 0.9% saline solution asa test liquid of at least 8 g/g.
 32. The non-woven absorbent fabric ofclaim 20, wherein the gelling fiber has a fiber free absorbency of 0.9%saline solution as a test liquid of at least 2 g/g.
 33. A process forforming a non-woven absorbent fabric comprising: blending a gellingfiber with a reinforcing fiber through a card to form a fiber web,wherein the reinforcing fiber comprises no more than 30 weight percentof the fiber web; forming a non-woven fabric by needlebonding orthermally bonding the fiber web.